Polymerization



Patented Sept. 12, 1944 POLYMERIZATION Lewis A. Bannon, Cranford, N. J., assignorvto Standard Oil Development Company,-a corporation of Delaware No Drawing. Application September 25, 1940,

Serial No. 358,302

Claims. (01. 260-68315) This invention relates to the polymerization of ydrocarbons of the olefin series and other unsaturated compounds, and more particularly to the production of polymers of the lubricating oil range-by the use of a novel catalyst composition.

The use of gaseous boron fluoride for the polymerization of oleflns, especially branched chain oleflns, such as isobutylene, is well known. There are, however, certain disadvantages in the use of this catalyst. When it is attempted to polymerize the low molecular weight oleflns, such as propylene, it is impossible to produce polymers except at extreme conditions of temperature and pressure. In the case oi. isobutylene, it is difficult to control the degree of polymerization to prevent the formation of very high molecular weight polymers. It is also difficult and costly to recover the boron fluoride catalyst. It is therefore a particular object of the present invention to provide a catalyst composition which will promote the polymerization of oleflns, especially the lower oleflns, at ordinary temperatures and pressures, and which will permit the formation of comparatively low molecular weight polymers of the lubricating oil range which will not be contaminated with high molecular weight polymers; It is a further object to provide a novel and efficient method for polymerizing aliphatic unset urated compounds generally to form products of the lubricating oil range. It is a stillfurther object of the invention to provide a catalyst which can be very readily separated from the product and returned to the reaction zone.

The new catalyst of the present invention consists of a liquid comprising boron fluoride and water. In general, it is preferred to use a composition in which the amount of water present varies from one to flve mols per mol of boron fluoride. The catalyst is readily prepared by bubbling boron fluoride gas into water. while keeping the mixture cool with ice or rapidly circulating cold water. By the use of this boron fluoridewater catalyst it is possible to polymerize low molecular weight oleflns, such as ethylene and propylene, at ordinary temperatures to give good yields of polymers suitable for use as lubricating oils. Higher molecular weight polymers may, on the other hand, he produced by employing sub normal temperatures. This catalyst has a further great advantage in the fact that it readily separates from the polymer product and may be returned for further use. costly means for removing boron fluoride gas from the product are thus avoided.

Troublesome and The present invention is applicable to the polymerization, not only of the lower molecular weight oleflns, but also higher molecular weight materials, such as unsaturated polymers and cracked wax, also dioleflns and unsaturated aliphatic compoundsjgenerally, including unsaturated ali-' phatic hydrocarbons in which one or more hydrogen atoms have been substituted with halogens, inorganic acid radicals or organic radicals of all types. Typical of this wider group of materialsare isoprene, methallyl chloride, methyl vinyl ketone, vinyl ethers and esters, and vegetable oils containing unsaturated fattycomphatic unsaturated compounds, for example, in

the copolymerization of acetylene with propylene V to form isoprene, as well as in the copolymerization of isobutylene with pentene, isobutylene with butadiene, isobutylene with corn oil, butadiene with acrylic nitrile, etc.

Temperature and pressure conditions are chosen so that the boron fluoride-water catalyst always remains in-the liquidphase. At atmospheric pressure a saturated solution of boron fluoride in water, i. e., a mixture containing a 1:1 ratio of water to boron fluoride, freezes at about 23 C. It is ordinarilydesirable,therefore, not to employ temperatures lower than about -20 C. 0n the other hand, temperatures as high as about 40 0., and even up to C.-under some conditions, may be used in the preparation of products in the lubricating oil boiling range from gaseous olefins. While these comparatively low temperatures favor the production of higher molecular weight products, such as lubricating oil,

of pressure may be employed, 1. e., from atmospheric up to 50 atmospheresor even higher. In general, increase of pressure increases the molecular weight of the productproduced at a given temperature. High pressures also increase the reaction rate.

It has been found that the viscosity index 01 the product varies somewhat with the temperature oi the reaction. For example, norma1 room temperatures seem to give the highest viscosiw, index oils from propylene, while the temperature giving'highest viscosity index oils irom normal butylene is about 65 C. V

The process oi this invention maybe readily carried out, in the case oi polymerization oi gaseous oleflns, by simply'bubbling the hydrocarbon through the liquid catalyst. The polymer product collects as an upper layer or emulsion and may be-removed and separated irom .the catalyst which is mixed or emulsified therewith by standing or by centrifuging. A suitable iorm oi apparatus is atower'either packed with glass or other suitable material or provided at the bottomwith a porous thimble for the introduction oi the hydrocarbon gas. The tower is pretverably surrounded with a cooling Jacket for the control oi the reaction temperature. The temperature may also be controlled by the use oi a diluent which boils at the reaction temperature 7 and pressure, such as butane, pentane, and other paraflins, or water itseli may be refluxed tothe reaction zone when the reaction is conducted.

under suitably high temperatures. Means are provided'i'or the removal oi the product at the side as it collects and ior the removal oi unreacted gases at the top. Themethod is well adapted for continuous operation, during which the olefln gas is continuously introduced into the tower, and the product is continuously re- ,moved and separated from entrained catalyst solution, the latter being separated irom the product and returned continuously or intermittently. Meansmay beprovided for continuously adding fresh boron fluoride to make up ior small losses occurring during the process. I

In cases where a liquid olefin material is to be polymerized, the reaction may also be carried out by adding the liquid gradually to the catalyst solution while maintaining vigorous agitation.

The process oi the present invention may be illustrated by the following examples:

Exams: 1

A reaction was carried out in accordance with the general procedure describedabove by passing propylene through a thimble into a tower containing a boron fluoride-water mixture containing one moi oi water per moi of boron fluoride. The reaction was continued ior about six daysat atmospheric pressure at a temperature varying irom 20 to 26 C'. The catalyst which was removed with the product was separated by standing and returned to the reactor intermittently. Toward the end oi the run the catalyst became somewhat weakened and the reaction rate was reduced. The total-product at the end of the run represented a yield oi 80% based upon the propylene feed. The polymer was. steam distilled up to 200 0.. The residue, representing a yield of 41% oi oil based on the total polymer product, had a Saybolt viscosity oi 662.4 seconds at 100 F. and 66.1 seconds at 210 F. and

a viscosity index of 78. For comparison, propylene and gaseous boron fluoride were simultaneously led into carbon tetrachloride at room temperatureior several hours. Only a trace oi polymer was formed,

Exams: 2

In three batch runs propylene was passed through a porous thimble into a tower which mmtained at. pressures 1 the nelghbory hood oi 100 pounds per'square inch and attemperatures oi 25, 39 and C., as shown by the accompanying table. The tower contained a boron fluoride-water catalyst'having a boron fluoride-water ratio of 1:1. In each case the propy lene was bubbled in continuously during the run, and the, productwas allowed to accumulate in the topoi the tower and was removed at the 7 end of the run. The product was separated from the aqueous catalyst by standing and was steam distilled up to 200C. The residue was testedv for its viscosity characteristics with the results as shown in the table below. The products from the runs conducted at 39 and 55 C.. aiter being separated from the catalyst, were washed with an aqueous caustic solution before being steam distilled. The yields were not determined accurately, but were oi the order oi that obtained in Example 1. conditions, time of run and properties of the tower containing a boron fluoride-watercatalyst having a ratio oi one mol oi boron fluoride to one mol oi water at atmospheric pressure and at a temperature oi 3 to 10 C. The product was separated irom the catalyst and vacuum distilled up-to 180 C. at 5 mm. pressure. The residue was an oil having a Saybolt viscosity oi 894.2 seconds at F. and 57.5 seconds at 210' I". and a vis-v cosity index oi '70. The yield was oi the order oi that obtained in Example 1. For comparison.

'an attempt was made to polymerize pentene by treating with boron fluoride gas for several hours.

Only a trace oi polymer was iormed.

This invention is not to be considered as limited by any oi the examples described above, which are given for illustrative purposes only. but is limited only by the terms oi the appended claims.

I claim: V 1. A process ior the polymerization oi oleflnsto iorm a product having a viscosity at least as high as that oi a lubricating oil which comprises contacting the oleflns at a temperature below .40 C. with a liquidcatalyst comprising boron fluoride and water.

2. A process for the polymerization of oleflns to iorm a product having a viscosity at least as high as that oi a lubricating oil which comprises contacting the oleflns at a temperature below 40 C. with a liquid catalyst consisting oi, one

molecular proportion oi boron trifluoride and one to flve molecular proportions oi water.

3. A process for the polymerization of oleflns to iorm a product of the lubricating oil range which comprises contacting the oleflns at a tem- The temperature and pressure perature below 40 C. with a liquid catalyst comprising boron fluoride and water at a pressure from 1 to 50 atmospheres.

4. A prbcess for the polymerization of olefincontaining gases resulting from the cracking of hydrocarbon oils to form a product of the lubricating oil range which comprises bubbling an olefin-containing gas into a reaction chamber containing a liquid catalyst at a temperature below 40 C., said catalyst consisting of one molecular proportion of boron trifluoride and from one to five molecular proportions of water.

5. A process for the continuous polymerization of olefin-containing gases resulting from the cracking of hydrocarbon oils to form a product 01' the lubricating oil range which comprises continuously bubbling an olefin-containing gas into a reaction chamber containing a liquid catalyst at a temperature below 40 C., said catalyst consisting of one molecular proportion of boron trifluoride and from one to five molecular proportions of water, and continuously removingirom.

water in the ratio of one mol of boron' fluoride to 80 water.

one 156 five mols of water, at a pressure of 1 to 50 atmospheres and a temperature higher than -20 C. but lower than 40 C.

'7. A process for the polymerization of normally gaseous olefins to form a product having a viscosity at least as high as that of a lubricating oil which comprises contacting the oleflns with aliquid catalyst consisting of boron fluoride and water in the ratio of about one mol of boron fluoride to one mol of water, at atmospheric pressure and at a temperature higher than -20 C. but lower than 40 C.

8. A process for producing a lubricating oil from propylene which comprises contacting the propylene with a liquid catalyst consisting of boron fluoride and water in the ratio of about one mol of boron fluoride to one mol of water, at

15 atmospheric pressure and at a temperature of 20 to 25 C.

, 9. A process for the polymerization of com- 20 as that of a lubricating oil which comprises contacting the said compounds at a. temperature below 40 C. with a liquid catalyst comprising boron fluoride and water. 1

10. A process for the polymerization of oleflns -25 to form a product of the lubricating oil range which comprises contacting the olefins at a temperature below 40 C. with a liquid catalyst consisting of one molecular Proportion of boron trifluoride and one to two molecular proportions of LEWIS A. BANNON. 

